Defoamers for aqueous systems

ABSTRACT

The products of the reaction of epichlorohydrin and compounds having the formula II 
     
       
         R 3 (EO) n (PO) m OH  (II) 
       
     
     wherein R 3  is an alkyl alkenyl or arenyl group having from 4 to 22 carbon atoms; a substituted alkyl or alkenyl group having from 4 to 22 carbon atoms wherein; n is a number from 0 to 50 and m is a number from 0 to 50; wherein the mole ratio of epichlorohydrin to (II) is from about 0.60/1 to about 2/1 are used in defoaming compositions for defoaming aqueous systems such as latex paints.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of application Ser. No.09/093,810, filed on Jun. 9, 1998, which also claims the benefit ofprovisional application Ser. No. 60/049,338, filed on Jun. 10, 1997.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not Applicable.

BACKGROUND OF THE INVENTION

Aqueous compositions such as polymer latexes and latex paints exhibit atendency toward foaming because they contain surface active agents suchas soaps, and synthetic detergents. In many instances, such compositionsproduce excessive foam and the user must use substances known asanti-foaming agents or defoamers. Some defoamers such as silicones tendto interfere with the function of these compositions in that theyinterfere with the basic function of a product such as a water-basedpaint after it has been deposited on a surface. Defoamers comprised ofwaxes dispersed in paraffin oil have been in aqueous systems such aslatexes and latex paints. These types of defoamers suffer from a numberof deficiencies such as poor defoaming or their defoaming effect isrelatively short-lived, and a tendency to reduce the scrub resistance ofpaints in which they have been used.

SUMMARY OF THE INVENTION

The surprising discovery has been made that the products of the reactionof epichlorohydrin and compounds having the formula II

R₃(EO)_(n)(PO)_(m)—OH  (II)

wherein R₃ is an alkyl, alkenyl or arenyl group having from 4 to 22carbon atoms; a substituted alkyl or alkenyl group having from 4 to 22carbon atoms wherein; n is a number from 0 to 50 and m is a number from0 to 50; wherein the mole ratio of epichlorohydrin to (II) is from about0.60/1 to about 2/1 are extremely efficient defoamers for aqueoussystems such as latexes and latex paints. These reaction products areadded to the aqueous systems in an amount sufficient to reduce oreliminate foam.

Another aspect of the invention pertains to a multi-component defoamerfor aqueous systems such as latexes and latex paints. Themulti-component defoamer according to the invention is a compositioncomprised of a hydrophobic solid, one or more reaction productsaccording to the invention dispersed and an inert water-insoluble liquidcarrier such as a paraffin oil. These defoamers exhibit enhanceddefoaming properties and good persistence in paints into which they havebeen added.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

Not Applicable.

DETAILED DESCRIPTION OF THE INVENTION

The term defoamer as used herein includes the reduction and/orprevention of foam or foaming in aqueous systems. An aqueous system isany aqueous medium such as an aqueous solution, dispersion or emulsion.The reaction products as described herein below can be used as defoamersfor aqueous systems in several ways. One way is by adding the reactionproducts themselves to an aqueous system such as a latex or a latexpaint in an amount effective to eliminate or decrease the foam generatedas a result of some type of mechanical action such as mixing, pouring,applying to a surface such as by a brush or a roller, and/or shaking.The amount required to eliminate and/or decrease foam is defined as adefoaming effective amount and will vary from one instance to anotherdepending upon the nature of the aqueous system and the defoaming effectdesired. A defoaming effective amount will be readily determinable byone of ordinary skill in the art will typically vary from about 0.001%to about 10.0%, preferably from about 0.1% to about 3.0% by weight.

Another way is by adding to an aqueous system a mixture comprised of oneor more reaction products according to the invention and a carrier oilbase. The carrier oil base useful in the process according to theinvention is any water-insoluble liquid that will dissolve and/ordisperse one or more reaction products according to the invention. Suchcarrier bases include but are not limited to paraffinic and naphthenicoils, tall oil fatty acids and alkoxylated tall oil fatty acids, fattyalcohols and alkoxylated fatty alcohols, liquid polypropylene oxide,liquid polyethylene oxide, liquid poly(ethylene oxide-propylene oxide)or any combination thereof. The relative amount of reaction productsaccording to the invention in the mixture with the carrier oil base willtypically range from about 1% to about 50% by weight and will preferablybe from about 1% to about 20% by weight. A defoaming effective amount ofsuch a mixture will be readily determinable by one of ordinary skill inthe art and will typically vary from about 0.01% by weight to about 10%,preferably from about 0.1 to about 2.0% by weight.

Yet another way of using the reaction products according to theinvention in defoaming applications is as part of a multi-componentdefoamer composition comprised of a hydrophobic solid and one or morereaction products according to the invention dispersed in an inert,water insoluble carrier fluid. The hydrophobic solid is any solid thatis insoluble in the carrier fluid and having a particle size of lessthan about 70 microns. Examples of the hydrophobic solid include, butare not limited to, waxes such as polyethylene wax,ethylene-bis-stearamide; inorganic powders such as silica. Mixtures ofvarious types of hydrophobic solids can also be used. The carrier fluiduseful in the processes and compositions according to the invention isany water-insoluble liquid that such as paraffin oil, naphthenic oils,liquid hydrocarbons, tall oil fatty acids and alkoxylated tall oil fattyacids, fatty alcohols and alkoxylated fatty alcohols, liquidpolypropylene oxide, liquid polyethylene oxide, liquid poly(ethyleneoxidepropylene oxide), or any combination thereof. A defoaming effectiveamount of such a multi-component defoamer composition will be readilydeterminable by one of ordinary skill in the art and will typically varyfrom about 0.1% by weight to about 10%, preferably from about 0.1 toabout 1.0% by weight.

This embodiment of the defoamer according to the invention can be madeby mixing one or more reaction products according to the invention, ahydrophobic solid and a water-insoluble liquid carrier capable ofdissolving or dispersing the hydrophobic solid and the reaction productat a temperature sufficient to melt the hydrophobic solid. Preferably,the above process can be modified by using a portion of the liquidcarrier in the mixing step followed by the addition of the warm mixtureto a second portion of liquid carrier at room temperature.

The reaction products according to the invention are the products of thereaction of epichlorohydrin and compounds having the formula II

R₃(EO)_(n)(PO)_(m)OH  (II)

wherein R₃ is a substituted or unsubstituted, saturated or unsaturatedaliphatic moiety having from 4 to 22 carbon atoms; a substituted alkylor alkenyl group having from 4 to 22 carbon atoms wherein; n is a numberfrom 0 to 50 and m is a number from 0 to 50; and epichlorohydrin whereinthe mole ratio of epichlorohydrin to (II) is from about 0.60/1 to about2/1 and preferably from about 0.80/1 to about 2/1. These products aredescribed in copending application Ser. No. 08/783,224, filed on Jan.14, 1997 (now U.S. Pat. No. 5,827,453).

In regard to the alkoxylates of formula 11, % can be any substituted orunsubstituted, saturated or unsaturated aliphatic moiety having from 4to 22 carbon atoms. Thus R₃ can be a linear or branched alkyl group, alinear or branched alkenyl or alkynyl group, a saturated carbocyclicmoiety, an unsaturated carbocyclic moiety having one or more multiplebonds, a saturated heterocyclic moiety, an unsaturated heterocyclicmoiety having one or more multiple bonds, a substituted linear orbranched alkyl group, a substituted linear or branched alkenyl oralkynyl group, a substituted saturated carbocyclic moiety, a substitutedunsaturated carbocyclic moiety having one or more multiple bonds, asubstituted saturated heterocyclic moiety, a substituted unsaturatedheterocyclic moiety having one or more multiple bonds. Examples of theabove include but are not limited to an alkyl group having from 4 to 22carbon atoms, an alkenyl group having from 4 to 22 carbon atoms, analkynyl group having from 4 to 12 carbon atoms. R₃ can also be an arenylgroup. Arenyl groups are 10 alkyl-substituted aromatic radicals having afree valence at an alkyl carbon atom such as a benzylic group. Thepreferred value of R₃ is an alkyl group having from 4 to 22 carbon atomsand most preferably an alkyl group having from 8 to 10 carbon atoms. Thedegree of ethoxylation is preferably from 2 to about 50 with the mostpreferred being from about 4 to about 50 while the degree ofpropoxylation can vary from 0 to 50. The degree of propoxylation will bedetermined by the desired degree of water solubility or miscibility. Thewater solubility or miscibility will ultimately be determined by suchfactors as the number of carbon atoms in R₃, the relative amounts EO toPO and the effect of PO on the biodegradability of the final defoamer.The water solubility or miscibility of a defoamer according to theinvention and the interrelationships between the number of carbon atomsin R₃, the relative amounts EO and PO and the biodegradability of thefinal product will be readily determinable by one of ordinary skill inthe art.

The method according to the invention can be used to control foamgenerated by any type of aqueous system having a surface tension belowthat of water such as aqueous-based personal care products as shampoos,facial cleaners, liquid hand soaps, and the like, and polymer latexesand latex paints. The defoaming compositions and methods are especiallyuseful for controlling foam in polymer latexes and latex paints.

The following examples are meant to illustrate but not to limit theinvention.

EXAMPLE 1

About 150 grams of decyl alcohol ethoxylated with an average of 4 molesof ethylene oxide (0.45 OH equivalents) were mixed with 385 grams oftoluene and 54 grams of 50% aq. NaOH (0.675 equivalents). The water wasremoved by azeotropic distillation and when a moisture level of lessthan 0.8% was reached, about 46 grams (0.51 equivalents) ofepichlorohydrin were slowly added. This mixture was allowed to react at100-110° C. for 24 hours. An aliquot of this mixture was removed andfiltered to remove the NaCl and vacuum stripped to remove the toluene togive an amber, easily pourable liquid product that was dispersible inwater. When about 1 gram of this liquid was shaken with 1 gram of decylalcohol ethoxylated with an average of 4 moles of ethylene oxide in 50grams of DI water, very little foam was observed. When 1 gram of decylalcohol ethoxylated with an average of 4 moles of ethylene oxide in 50grams of DI water was shaken, a very large amount of foam was observed.

EXAMPLE 2

About 51 grams of butanol ethoxylated with an average of 2 moles ofethylene oxide (0.32 OH equivalents) were mixed with 120 grams oftoluene and 25 grams of 50% aq. NaOH (0.32 equivalents). The water wasremoved by azeotropic distillation and when a moisture level of lessthan 0.8% was reached, about 46 grams (0.24 equivalents) ofepichlorohydrin were slowly added. This mixture was allowed to react at100-110° C. for 24 hours. An aliquot of this mixture was removed andfiltered to remove the NaCl and vacuum stripped to remove the toluene togive an amber, easily pourable liquid product that was insoluble inwater. When about 1 gram of this liquid was shaken with 1 gram of decylalcohol ethoxylated with an average of 4 moles of ethylene oxide in 50grams of DI water, very little foam was observed.

EXAMPLE 3

About 200 (0.654 hydroxy) of octyl ethoxylated with an average of 4moles of ethylene oxide was mixed with 400 gm toluene and 78.4 gm (0.98equivs.) of 50% NaOH. Water was removed by azeotropic distillation untilthe level was below 0.8%. The mixture was cooled to 80° C. and 67.2 gm(0.72 moles) of epichlorohydrin was added over 45 mins. The mixture wasstirred for 24 hrs at 110° C. until the epoxy titration showed noepoxide left. The material was cooled, filtered and the toluene wasremoved by vacuum distillation leaving a dark brown low viscosityliquid.

EXAMPLE 4

To a 1000 ml flask, 686 gms (2.0 OH equivs) of TRYCOL® 5950(Decylalcohol+4 moles EO) was added. Material was warmed to 70° C. Atthis time 211 gms (2.6 equiv.) of 50% aqueous sodium hydroxide was addedslowly over 2 hrs by drop from an addition funnel while pulling fullvacuum, heating to 140° C., and distilling off water. After approx., 5hrs, all the NaOH was in and no more water was distilling off, thereaction was cooled to 70° C. An addition funnel containing 208 gms (2.2moles) of epichlorohydrin was attached and allowed to drip in over 1.5hrs maintaining the exotherm below 110° C. After the epichlorohydrin hadbeen added, the temperature was raised to 120° C. until the oxiranetitration indicated all the epichlorohydrin had reacted (approx. 12hrs). At this point the salt was removed via water washing,centrifugation, filtration, Electro Dialysis or any combination of theseleaving a dark amber liquid. The material can be lightened from aGardner 14 to a Gardner 5 or lower with peroxide or Magnesol.

EXAMPLE 5

The procedure of Example 4 was repeated except that sodium hydroxide wasreplaced with sodium methoxide and methanol was distilled off.

EXAMPLE 6

To a 1000 ml flask, 686 gms (2.0 OH equivs) of TRYCOL® 5950 was added,heated to 80° C. and dried under vacuum. Then 208 gms (2.2 moles) ofepichlorohydrin added. A total of 4 gms of boron trifluoride etheratewas added in 4-1 gm parts, each after the previous exotherm subsides andan oxirane titration indicates there was still some unreacted oxirane.When no oxirane remains, 211 gms (2.6 equivs) of 50% NaOH was added over2 hrs by addition funnel, under full vacuum, while heating to 140° C.and distilling off water. After no more water was being distilled, thematerial was cooled. At this point the salt was removed via water wash,centrifugation, filtration or any combination of these leaving a cleardark amber liquid. This material can be lightened with peroxide orMagnesol or any other known method.

EXAMPLE 7 DEFOAMER PERFORMANCE TEST METHODS FOR EVALUATIONS IN PAINTS

A. DEFOAMER ACTIVITY TEST—RED DEVIL SHAKER METHOD MATERIAL & EQUIPMENT

Red Devil Shaker (Model 5110-X)

2 pint paint cans

Paint gravity cup (weight per gallon cup)

Balance (500 gm. capacity min., accurate to “0.01 gm)

Test medium—standard batch of defoamer-free paint (also free ofentrained air)

Defoamer reference “standard”

Defoamer to be evaluated

PROCEDURE

1. Weigh 125 cc sample of test paint into 2 pint (250 cc) paint can.

2. Add defoamer being evaluated at a level of 0.5% by weight based onweight of paint.

3. Seal can and place on outer-most edge of Red Devil Paint Shaker Clamp(farthest from axis of rotation) so that maximum arc is achieved.

NOTE: Cans must be placed in identical location on clamp for each test.

4. Shake for 5 minutes. Immediately after shaking, determine theweight/gallon of the shaker paint sample.

5. The decrease in density compared with that of the unshaken controlpaint sample is regarded as the amount of foam generated.${\% \quad {AIR}\quad {ENTRAINED}} = \frac{\begin{matrix}{{{{wt}.\text{/}}{{gal}.\quad \left( {{unshaken}\quad {control}} \right)}} -} \\{{wt}\text{/}{{gal}\left( {{test}\quad {sample}\quad {with}\quad {defoamer}} \right)}}\end{matrix}}{{wt}.\quad {gal}.\quad \left( {{unshaken}\quad {control}} \right)}$

NOTE:

1. A shaken blank (standard paint without defoamer) should be run foreach batch of standard test paint to determine the “foaminess” of thetest medium and to establish the general magnitude of defoamer activity.

2. When comparing a sample of a given defoamer with a “standard”, thestandard should be re-run side by side with the test sample each time.It should be noted that depending on the test medium being used,variations of several percent entrained air between acceptable defoamersamples are not unusual.

B. DEFOAMER ACTIVITY TEST—ROLLER APPLICATION MATERIAL & EQUIPMENT

3″ roller handle

3″ roller cover, 3/8″ nap

roller pan

Sherwin Williams Test Paper

Shurline Brush & Roller Cleaner

PROCEDURE

1. Pre-soak 3″ roller cover in distilled water and then spin dry using10 strokes on Shurline Brush & Roller Cleaner.

2. Pour entire contents of 2 pint paint cans used in Test A (ShakerTest) into roller pan and saturate ⅜″ nap roller.

3. Apply paint to 12″×13″ sheet of Sherwin Williams paper mounted in avertical position. Roller application technique should be consistentfrom test to test.

4. Immediately upon completion of roll-out, observe rate of bubblebreak.

5. Examine dry roll-outs for cratering resulting from delayedbubblebreak.

Roll-outs resulting from various defoamers as well as a blank may berated relative to each other.

C. DEFOAMER COMPATIBILITY TESTS MATERIAL & EQUIPMENT

Leneta form 2C sealed opacity charts

Bird Perforated Vacuum Plate

Bird Film Applicator 6″, to deposit 3 mil wet film

PROCEDURE

1. Apply Leneta Opacity Chart to vacuum plate so that chart is held flatand firm against plate.

2. Pour contents of paint gravity cup (following each Shaker Test—TestA) onto Leneta Opacity Chart and drawdown using Bird Film Applicator toyield a 3 mil wet paint film.

3. Observe film for film irregularities such as fisheyes, orange-peel,crawling or other defoamer related defects.

4. If paint system is tinted, a “rub-up test” should be performedwhereby a portion of the wet draw-down is rubbed with the finger in acircular motion until tacky or near dry. Any difference in color orintensity of the rubbed-up area compared with the surrounding film isindicative of pigment flocculation which may be affected by thedefoamer.

HEAT AGING

Duplicate 2 pint cans are prepared (as in Test A, steps 1 and 2 followedby 5 minute stir-in of defoamer using a laboratory stirrer) for thosedefoamers which appear promising based on initial results. These cansare placed in an oven at 120° F. (49° C.). After two weeks at 120° F.,the samples are evaluated via tests A, B and C to determine the effectof prolonged storage of the paint/defoamer system.

EXAMPLE 8

A composition was prepared from the following components, in which thepolyethylene wax is dispersed in the mineral oil:

Component % by wt. Mineral oil 91 Polyethylene wax 7 Reaction product* 2*product of the reaction between C9-11 alkyl - (EO)₄OH andepichlorohydrin (epi:OH ratio of 1:1.1).

The above composition was prepared by first heating together 25 grams ofmineral oil, polyethylene wax, and the reaction product to a temperatureof 125-130° C. Then the resulting mixture was slowly added into 66 gramsof mineral oil at room temperature with high agitation.

The composition was added to a semi-gloss latex paint (VALSPAR® OB28177) in a concentration of 0.9% by weight. In 155 seconds all bubblespresent in the latex paint were broken.

A similar composition prepared as above except that no reaction productwas present in the composition was added to another sample of the abovelatex paint in a concentration of 0.9% by weight. After 300 seconds someof the bubbles present in the latex paint were still not broken.

When the pure reaction product itself was added to another sample of thelatex paint in a concentration of 0.9% by weight, after 300 seconds someof the bubbles present in the latex paint were still unbroken.

EXAMPLE 9

A composition was prepared similar to that of Example 8 except that thecomposition contained 89% of mineral oil, 7% polyethylene wax, and 4%reaction product.

EXAMPLE 10

A composition was prepared from the following components wherein the waxbecomes dispersed in the mineral oil:

Component % by wt. Mineral oil 91 Ethylene bis-stearamide 5 wax (EBSwax) reaction product* 4 *reaction product used in Example 8

EXAMPLE 11

A number of compositions were prepared according to the process ofExample 8 containing 3% by weight of ethylene bis-stearamide wax andvarying quantities of the reaction product used in Example 8. Thesecompositions were added to samples of a semi-gloss latex paint (based onUCAR 379 latex). The compositions (defoamers) and the results obtainedare set forth in table 1 below:

TABLE 1 REACTION DEFOAMER PRODUCT COMPOSITION INITIAL BUBBLE BREAK CONC¹(WT. %) CONC² (WT. %) AIR % TIMES (SEC.) 0 0 0.39 >300 0 0.5 0 >300 0.50.5 0 >300 1 0.5 0 >300 2 0.5 0 >300 3 0.5 0 28 4 0.5 0 15 6 0.5 0 14 80.5 0 14 ¹in the defoamer composition ²in the latex paint.

It can be seen from the above Table 1 that at a defoamer compositionconcentration of only 0.5%, containing a reaction product concentrationof at least 3% by weight, the defoamer composition is highly effectivein defoaming latex paint.

EXAMPLE 12

This example shows the effectiveness of the reaction products ofepichiorohydrin and an alkoxylated alcohol as defoaming agents inpaints. The following reaction products were prepared according to theprocess of Example 1:

Example # Alcohol Moles of EO epi:OH mole ratio 12A C₉₋₁₁ 4 1.1:1 12BC₉₋₁₁ 8 1.1:1 12C C₉₋₁₁ 8 1.4:1 12D C₉₋₁₁ 4 0.8:1

The above reaction products were evaluated for their defoamingperformance using the test method of Example 7 and the results set forthin TABLE 2 below:

TABLE 2 ROHM AND HAAS ROVACE 661 (FORMULA 92110 A) WHITE FLAT PAINTBUBBLE BREAK DEFOAMER CONC. wt (%) % AIR TIME (SEC) NONE 0 17.2 >300 12A0.1 4.2 16 12B 0.1 2.2 8 12C 0.1 3.1 24 12D 0.1 5.1 >300

EXAMPLE 13

This example shows that the reaction products of the invention areeffective as defoaming agents at even lower concentrations when they arepresent in a water-insoluble liquid carrier fluid and a hydrophobicsolid insoluble in the carrier fluid.

4 Grams of the reaction product of epichlorohydrin and decyl alcohol·4EO(1.1:1 mole ratio), prepared according to the process of Example 1, wasmixed with about 7 grams of polyethylene wax (A-C 629, a trademarkedproduct of Allied Signal Corp) in about 25 grams of 100-105 secondparaffin oil (Saybolt −100° F.) grade and heated to 105° C. The heatedsolution was then mixed with about 64 grams of paraffin oil (Saybolt−100° F.) at room temperature with agitation to form a dispersion of thewax in the oil.

Defoaming results of the wax dispersion containing the above reactionproduct were compared to the wax dispersion alone, and the reactionproduct alone. The results are set forth in Table 3 below.

EXAMPLE 14

This example shows that other hydrophobic waxes are also effective whenpresent in the paraffin oil containing the reaction product used inExample 13.

4 Grams of the reaction product of epichlorohydrin and decyl alcohol·4EO(1.1:1 mole ratio) was mixed with 5 grams of ethylenebisstearamide (EBS)wax and about 29 grams of paraffin oil (Saybolt −100° F.), heated to145° C. until the wax dissolved, and then added to 61.6 grams of theabove paraffin oil at room temperature with stirring. A dispersion ofthe wax in the oil was obtained. Further reduction of the particle sizeof the wax can be obtained, if desired, by use of a homogenizer. Resultsof defoaming effectiveness are also set forth in TABLE 3 below.

TABLE 3 Reaction Bubble Product Break Conc. Conc. Time DEFOAMER (wt. %)(wt. %) Air % (sec.) WHITE SEMI GLOSS PAINT BASED ON ROHM + HAAS RHOPLEXSG-10M LATEX Blank 0 0 4.5 >300 R.P.¹ 0.5 0.500 0.56 31 R.P 0.1 0.1000.1 154 PE Wax based² 0.5 0 1.2 >300 PE Wax base + 4% R.P. 0.5 0.0200.74 22 PE Wax base + 4% R.P. 0.1 0.004 1.4 62 EBS wax base 0.5 01.4 >300 EBS wax base + 4% R.P. 0.5 0.020 0.93 5 EBS wax base + 4% R.P.0.1 0.004 1.7 67 WHITE FLAT PAINT BASED ON UNION CARBIDE UCAR 379 LATEXBlank 0 0 4 >300 R.P.¹ 0.5 0.500 0 44 R.P 0.2 0.200 1.6 54 PE Wax based²0.5 0 1.1 >300 PE Wax base + 4% R.P. 0.5 0.020 0.8 61 PE Wax base + 4%R.P. 0.2 0.008 1.7 80 EBS wax base 0.5 0 1.2 227 EBS wax base 0.2 01.8 >300 EBS wax base + 4% R.P. 0.5 0.020 1.5 99 EBS wax base + 4% R.P.0.2 0.008 1.5 92

EXAMPLE 15

This example shows that even where the reaction product is ineffectivein very small concentrations, it can be highly effective in even smallerconcentrations when present in a water-insoluble liquid carrier fluidand a hydrophobic solid insoluble in the carrier fluid.

The composition of Example 13 was formulated except that the alkoxylatedalcohol in the reaction product was C₉₋₁₁ alcohol·8EO instead of decylalcohol·4EO. The defoaming results are set forth in TABLE 4 below.

TABLE 4 WHITE SEMI-GLOSS PAINT BASED ON UNION CARBIDE UCAR 379 LATEXReaction Bubble Product Break Conc. Conc. Time DEFOAMER (wt. %) (wt. %)Air % (sec.) None 0 0 6.6 >300 R.P. 0.1 0.10 5.8 >300 PE base + 4% R.P.0.5 0.02 2.4 5

EXAMPLE 16

This example shows that other properties of paint, such as gloss, can beimproved by changing or diluting the carrier fluid with a differentfluid material.

The defoamer composition of example 13 was diluted with UCON LB-65(polypropyleneoxide from Union Carbide) at a ratio of 30 parts by weightof the defoamer composition of example 17 to 70 parts by weight ofpolypropyleneoxide. This blend improved gloss as shown in TABLE 6 below.

TABLE 6 HIGH GLOSS WHITE PAINT BASED ON ROHM + HAAS HG-95 LATEX BubbleBreak Conc. Time 20° 60° DEFOAMER (wt. %) Air % (sec.) Gloss Gloss None0 9.1 >300 58 82 Example 13 0.5 1.0 7 36 71 Example 16 0.5 0.8 26 47 75

What is claimed is:
 1. A process for reducing or preventing foam in anaqueous system comprising adding to the aqueous system from about 0.001%to about 10.0% by weight of a composition which is the product of theprocess which comprises reacting epichlorohydrin and a compound of theformula II R₃(EO)_(n)(PO)_(m)OH  (II) wherein R₃ is a saturated orunsaturated organic group having from 4 to 22 carbon atoms; n is anumber from 0 to 50 and m is a number from 0 to 50; wherein the moleratio of epichlorohydrin to (II) is from about 0.60/1 to about 2/1. 2.The process of claim 1 wherein R₃ is an alkyl group having from 4 to 12carbon atoms.
 3. The process of claim 1 wherein R₃ is an alkyl grouphaving from 8 to 10 carbon atoms.
 4. The process of claim 1 wherein n isa number from about 2 to about
 50. 5. The process of claim 1 wherein nis a number from about 4 to about
 50. 6. The process of claim 1 whereinthe mole ratio of epichlorohydrin to (II) is from about 0.80/1 to about2/1.
 7. The process of claim 1 wherein R₃ is an alkyl group having from4 to 12 carbon atoms and n is a number from about 2 to about
 50. 8. Theprocess of claim 1 wherein R₃ is an alkyl group having from 8 to 10carbon atoms and n is a number from about 4 to about
 50. 9. The processof claim 1 wherein from about 0.1% to about 10% by weight of saidcomposition is added to the aqueous system.
 10. The process of claim 9wherein from about 0.1% to about 3% by weight of said composition isadded to the aqueous system.
 11. The process of claim 1 wherein R₃ is analkyl, alkenyl, alkynyl or arenyl group.
 12. The process of claim 1wherein R₃ is selected from the groups consisting of a linear orbranched alkyl group, a linear or branched alkenyl or alkynyl group, asaturated carbocyclic moiety, an unsaturated carbocyclic moiety havingone or more multiple bonds, a saturated heterocyclic moiety, anunsaturated heterocyclic moiety having one or more multiple Nonds, asubstituted linear or branched alkyl group, a substituted linear orbranched alkenyl or alkynyl group, a substituted saturated carbocyclicmoiety, a substituted unsaturated carbocyclic moiety having one or moremultiple bonds, a substituted saturated heterocyclic moiety, and asubstituted unsaturated heterocyclic moiety having one or more multiplebonds.
 13. A process for reducing or preventing foam in an aqueoussystem comprising adding to the aqueous system from about 0.01% to about10% by weight of a composition comprised of: (a) the product of theprocess which comprises reacting epichlorohydrin and a compound of theformula II R₃(EO)_(n)(PO)_(m)OH  (II) wherein R₃ is a saturated orunsaturated organic group having from 4 to 22 carbon atoms; n is anumber from 0 to 50 and m is a number from 0 to 50; wherein the moleratio of epichlorohydrin to (II) is from about 0.60/1 to about 2/1; and(b) a water-insoluble liquid carrier capable of dissolving or dispersingcomponent (a).
 14. The process of claim 13 wherein R₃ is an alkyl grouphaving from 4 to 12 carbon atoms.
 15. The process of claim 13 wherein R₃is an alkyl group having from 8 to 10 carbon atoms.
 16. The process ofclaim 13 wherein n is a number from about 2 to about
 50. 17. The processof claim 13 wherein n is a number from about 4 to about
 50. 18. Theprocess of claim 13 wherein the mole ratio of epichlorohydrin to (II) isfrom about 0.80/1 to about 2/1.
 19. The process of claim 13 wherein R₃is an alkyl group having from 4 to 12 carbon atoms and n is a numberfrom about 2 to about
 50. 20. The process of claim 13 wherein R₃ is analkyl group having from 8 to 10 carbon atoms and n is a number fromabout 4 to about
 50. 21. The process of claim 13 wherein the aqueoussystem is a latex paint.
 22. The process of claim 13 wherein thecompound of the formula II is C₁₀H₂₁O(EO)₈OH and the mole ratio ofepichlorohydrin to (II) is 1.1/1.0.
 23. The process of claim 13 whereinthe water-insoluble liquid carrier is selected from the group consistingof paraffin oil, naphthenic oils, liquid hydrocarbons, tall oil fattyacids and ethoxylated tall oil fatty acids, fatty alcohols andethoxylated fatty alcohols, liquid polypropylene oxide, liquidpolyethylene oxide, liquid poly(ethylene oxide-propylene oxide), andcombinations thereof.
 24. The process of claim 23 wherein thewater-insoluble liquid carrier is paraffin oil.
 25. The process of claim13 wherein R₃ is an alkyl, alkenyl, alkynyl or arenyl group.
 26. Theprocess of claim 13 wherein R₃ is selected from the group consisting ofa linear or branched alkyl group, a linear or branched alkenyl oralkynyl group, a saturated carbocyclic moiety, an unsaturatedcarbocyclic moiety having one or more multiple bonds, a saturatedheterocyclic moiety, an unsaturated heterocyclic moiety having one ormore multiple ponds, a substituted linear or branched alkyl group, asubstituted linear or branched alkenyl or alkynyl group, a substitutedsaturated carbocyclic moiety, a substituted unsaturated carbocyclicmoiety having one or more multiple bonds, a substituted saturatedheterocyclic moiety, and a substituted unsaturated heterocyclic moityhaving one or more multiple bonds.
 27. The process of claim 13 whereinfrom about 0.1% to about 2.0% by weight of said composition is added tothe aqueous system.
 28. A process for reducing or preventing foam in anaqueous system comprising adding to the aqueous system from about 0.1%to about 10% by weight of a composition comprised of (a) the product ofthe process which comprises reacting epichlorohydrin and a compound ofthe formula II R₃(EO)_(n)(PO)_(m)OH  (II) wherein R₃ is a saturated orunsaturated organic group having from 4 to 22 carbon atoms; n is anumber from 0 to 50 and m is a number from 0 to 50; wherein the moleratio of epichlorohydrin to (II) is from about 0.60/1 to about 2/1; (b)a hydrophobic solid; and (c) a water-insoluble liquid carrier capable ofdissolving or dispersing component (a).
 29. The process of claim 28wherein R₃ is an alkyl group having from 4 to 12 carbon atoms.
 30. Theprocess of claim 28 wherein R₃ is an alkyl group having from 8 to 10carbon atoms.
 31. The process of claim 28 wherein n is a number fromabout 2 to about
 50. 32. The process of claim 28 wherein n is a numberfrom about 4 to about
 50. 33. The process of claim 28 wherein the moleratio of epichlorohydrin to (II) is from about 0.80/1 to about 2/1. 34.The process of claim 28 wherein R₃ is an alkyl group having from 4 to 12carbon atoms and n is a number from about 2 to about
 50. 35. The processof claim 28 wherein R₃ is an alkyl group having from 8 to 10 carbonatoms and n is a number from about 4 to about
 50. 36. The process ofclaim 28 wherein the aqueous system is a latex paint.
 37. The process ofclaim 28 wherein the compound of the formula II is C₁₀H₂₁O(EO)₈OH andthe mole ratio of epichlorohydrin to (II) is 1.1/1.0.
 38. The process ofclaim 28 wherein the water-insoluble liquid carrier is selected from thegroup consisting of paraffin oil, naphthenic oils, liquid hydrocarbons,tall oil fatty acids and ethoxylated tall oil fatty acids, fattyalcohols and ethoxylated fatty alcohols, liquid polypropylene oxide,liquid polyethylene oxide, liquid poly(ethylene oxide-propylene oxide),and combinations thereof.
 39. The process of claim 28 wherein thewater-insoluble liquid carrier is paraffin oil.
 40. The process of claim28 wherein the hydrophobic solid is selected from the group consistingof a polyethylene wax, ethylene bis-stearamide and combinations thereof.41. The process of claim 40 wherein the hydrophobic solid ispolyethylene wax.
 42. The process of claim 28 wherein R₃ is selectedfrom the group consisting of a linear or branched alkyl group, a linearor branched alkenyl or alkynyl group, a saturated carbocyclic moiety, anunsaturated carbocyclic moiety having one or more multiple bonds, asaturated heterocyclic moiety, an unsaturated heterocyclic moiety havingone or more multiple ponds, a substituted linear or branched alkylgroup, a substituted linear or branched alkenyl or alkynyl group, asubstituted saturated carbocyclic moiety, a substituted unsaturatedcarbocyclic moiety having one or more multiple bonds, a substitutedsaturated heterocyclic moiety, and a substituted unsaturatedheterocyclic moiety having one or more multiple bones.
 43. The processof claim 28 wherein R₃ is an alkyl, alkenyl, alkynyl or arenyl group.44. The process of claim 28 wherein from about 0.1% to about 1.0% byweight of said composition is added to the aqueous system.